WO2024070735A1 - Matériau composite métal/composé organique - Google Patents

Matériau composite métal/composé organique Download PDF

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Publication number
WO2024070735A1
WO2024070735A1 PCT/JP2023/033566 JP2023033566W WO2024070735A1 WO 2024070735 A1 WO2024070735 A1 WO 2024070735A1 JP 2023033566 W JP2023033566 W JP 2023033566W WO 2024070735 A1 WO2024070735 A1 WO 2024070735A1
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Prior art keywords
organic compound
metal
particles
metal material
compound
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PCT/JP2023/033566
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English (en)
Japanese (ja)
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貴之 湖山
弘高 伊藤
慎太郎 山本
翔生 桂
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株式会社神戸製鋼所
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Publication of WO2024070735A1 publication Critical patent/WO2024070735A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/04—Metals; Alloys
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/40—Lubricating compositions characterised by the base-material being a macromolecular compound containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials

Definitions

  • This disclosure relates to metal-organic compound composites.
  • Metal materials can be used for sliding components such as machine parts, such as bearings, piston rings, and cylinders, as well as mold parts used in press processing, etc.
  • Sliding components are required to have lubricity (i.e. a low coefficient of friction) since they are subjected to repeated sliding on a daily basis.
  • Patent Document 1 discloses that a solid lubricant is brought into contact with a metal material (specifically, that the solid lubricant is uniformly dispersed in the metal material), and that talc is preferable as the solid lubricant from the viewpoint of lubricity, etc.
  • Patent Document 2 discloses that an inorganic filler such as talc is brought into contact with the metal material (co-deposition) in order to impart lubricity to the metal material.
  • This disclosure has been made in light of these circumstances, and one of its objectives is to provide a metal material (or a composite material thereof) with improved lubricity compared to conventional techniques.
  • the plurality of organic compound particles include a state in which the metal material is attached to the surface of the metal material so as to be peelable with a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No.
  • the plurality of organic compound particles include at least one selected from the group consisting of compound A, compound B, and compound C;
  • the compound A is an aliphatic compound containing, in a unit molecular structure, two or more selected from the group consisting of hydrogen (H), carbon (C) and oxygen (O)
  • the compound B is an aliphatic compound containing one or more amide bonds in a unit molecular structure
  • the compound C is a metal-organic compound composite material, which is an aromatic compound containing one or more amino groups in its unit molecular structure.
  • Aspect 2 of the present invention is The metal-organic compound composite material according to aspect 1, wherein the plurality of organic compound particles include the compound A.
  • Aspect 3 of the present invention is The metal material contains more than 50 mass% in total of one or more metals selected from the group consisting of Al, Ti, Cu, Au, Sn, Zn, and Cr,
  • Aspect 4 of the present invention is The metal material contains more than 50 mass% in total of one or more metals selected from the group consisting of Al, Ti, Cu, Au, Ni, Sn, and Cr, The metal-organic compound composite material according to any one of Aspects 1 to 3, wherein the plurality of organic compound particles include the compound C.
  • Aspect 5 of the present invention is The metal-organic compound composite material according to any one of Aspects 1 to 4, wherein when the plurality of organic compound particles are subjected to a thermogravimetric differential thermal analysis from room temperature to a maximum of 1000° C. at a heating rate of 10° C./min, if a melting point is exhibited, the melting point is 100° C. or higher, or no melting point is exhibited.
  • Aspect 6 of the present invention is The metal-organic compound composite material according to any one of Aspects 1 to 5, wherein when the plurality of organic compound particles are subjected to a thermogravimetric differential thermal analysis from room temperature to a maximum of 1000° C. at a heating rate of 10° C./min, if a decomposition point is exhibited, the decomposition point is 500° C. or less, and if a combustion point is exhibited but no decomposition point is exhibited, the combustion point is 500° C. or less.
  • Aspect 7 of the present invention is 7.
  • Aspect 8 of the present invention is 8.
  • Aspect 9 of the present invention is The metal-organic compound composite material according to any one of Aspects 1 to 8, wherein the plurality of organic compound particles are attached to the surface of the metal material so as to be peelable with a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No. 405).
  • a cellophane adhesive tape manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No. 405
  • Aspect 10 of the present invention is The metal-organic compound composite material according to any one of Aspects 1 to 8, wherein the organic compound particles are embedded in the metal material such that at least a portion of the metal material is exposed on the surface.
  • FIG. 1 shows a schematic cross-sectional view of an example of a metal-organic compound composite material according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view of another example of a metal-organic compound composite material according to an embodiment of the present invention.
  • 1 shows a photograph of the surface of a metal-organic compound composite material in which polyethylene oxide particles are brought into contact (adhered) with the surface of the metal material (Ni-P plating layer) produced in Example 1.
  • FIG. 2B shows a photograph of the metal-organic compound composite material after a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No.
  • FIG. 1 shows a schematic diagram of the surface of a sample that was subjected to a reciprocating sliding test. After a reciprocating sliding test was performed on the metal material in Table 1: Ni-P (without particles), the center of the sliding mark 30 as shown in FIG. 3A was measured with a surface roughness meter in a direction perpendicular to the sliding direction.
  • the surface profile result is shown in FIG. 1 shows a photograph of the surface of a metal-organic compound composite material in which polyethylene oxide particles are brought into contact (adhered) with the surface of the metal material (Ni-P plating layer) produced in Example 2.
  • the present inventors have studied from various angles in order to realize a metal composite material with improved lubricity compared to the conventional technology described in Patent Document 1.
  • lubricity was imparted by contacting talc or the like having a solid lubricating effect with a metal material.
  • talc which is an inorganic particle having a solid lubricating effect
  • the friction coefficient can be reduced (i.e., lubricity can be improved) compared to contacting talc.
  • the reaction film may contain atomic components of the metal material that are thought to diffuse into the film or originate from wear powder.
  • the metal-organic compound composite according to an embodiment of the present invention comprises:
  • the present invention includes a metal material containing more than 50 mass% of one or more metals selected from the group consisting of Al, Ti, Cu, Au, Ni, Sn, Zn, and Cr in total, and a plurality of organic compound particles, the plurality of organic compound particles being attached to the surface of the metal material so as to be peelable with a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No.
  • a cellophane adhesive tape manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No.
  • the plurality of organic compound particles including one or more selected from the group consisting of Compound A, Compound B, and Compound C,
  • Compound A being an aliphatic compound containing two or more selected from the group consisting of hydrogen (H), carbon (C), and oxygen (O) in its unit molecular structure
  • Compound B being an aliphatic compound containing one or more amide bonds in its unit molecular structure
  • Compound C being an aromatic compound containing one or more amino groups in its unit molecular structure.
  • FIG. 1A shows a schematic cross-sectional view of a metal-organic compound composite according to an embodiment of the present invention.
  • the metal-organic compound composite 1 includes a metal material 2 and a plurality of particles 3, and the plurality of particles 3 are embedded in the metal material 2 so that at least a portion 2a of the metal material 2 is exposed on the surface of the metal-organic compound composite 1 (so that the particles 3 do not cover the entire surface 2b of the metal material 2).
  • each particle 3 is partially embedded in the metal material 2, and the remaining portion is exposed on the surface of the metal-organic compound composite 1.
  • a part of a specific organic compound decomposes during sliding of the metal material 2, and a part of the decomposition forms a new reaction film containing carbon, thereby reducing the friction coefficient near the surface 2b of the metal material 2 and improving lubricity.
  • the initial contact resistance (electrical resistance) before sliding can be reduced when the metal-organic compound composite 1 is used as a contact material. Whether or not at least a portion 2a of the metal material 2 is exposed on the surface can be determined, for example, by visually checking whether or not there is metallic luster.
  • each particle 3 may be entirely embedded in the metal material 2 before the start of sliding. This allows the friction coefficient to be reduced, similar to the metal-organic compound composite 1, by performing a sliding process so that the particles 3 are exposed. Also, similar to the metal-organic compound composite 1, the initial contact resistance can be reduced.
  • particle 3 partly embedded in metal material 2 includes an embodiment in which a single particle 3 is entirely embedded in the metal material 2 before the start of sliding, but part of it is exposed from the metal material 2 after the start of sliding, and the remaining part is embedded in the metal material 2.
  • FIG. 1B shows a schematic cross-sectional view of another example of a metal-organic compound composite according to an embodiment of the present invention.
  • the metal-organic compound composite 11 includes a metal material 2 and a plurality of particles 3, and the plurality of particles 3 are attached to the surface 2b of the metal material 2.
  • the particles 3 are attached to the surface 2b with such a weak force that they can be peeled off with cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No. 405).
  • the multiple particles 3 are shown attached to the surface 2b of the metal material 2 so that the metal material 2 is not exposed on the surface of the metal-organic compound composite 1 between the multiple particles 3 (so that the entire surface 2b of the metal material 2 is covered), but this is not limited to the state, and for example, the metal material 2 may be attached to the surface 2b so that a part of the metal material 2 is exposed on the surface of the metal-organic compound composite 1 between the multiple particles 3.
  • the contact state of the particles 3 with the metal material 2 has been exemplified, but the contact state may be one type or two or more types.
  • a portion of the particles 3 may be attached to the surface of the metal material 2, and the remaining particles 3 may be embedded in the metal material 2.
  • the embedded state of the particles 3 a portion of the particles 3 may be exposed from the surface of the metal material 2, and the remaining particles 3 may be completely embedded in the metal material 2.
  • Metal material 2 contains more than 50 mass% in total of one or more metals selected from the group consisting of Al, Ti, Cu, Au, Ni, Sn, Zn, and Cr. Metal material 2 preferably contains 75 mass% or more of the metals in total, more preferably 85 mass% or more in total, and even more preferably 95 mass% or more in total. Metal material 2 may contain only one type of the above metal, or may contain two or more types.
  • the metal material 2 may be a bulk material or a surface treatment layer such as a plating layer.
  • the thickness t of the metal material 2 is not particularly limited. If the metal material 2 is a surface treatment layer such as a plating layer, t may be 0.05 ⁇ m or more, preferably 0.07 ⁇ m or more, and more preferably 0.10 ⁇ m or more. Also, t may be 100 ⁇ m or less, preferably 50 ⁇ m or less, and more preferably 30 ⁇ m or less.
  • organic compound particles 3 refers to compounds containing carbon, excluding compounds with simple structures such as carbon monoxide, carbon dioxide, carbonates, hydrocyanic acid, cyanates, thiocyanates, B 4 C, and SiC, etc.
  • a silicone resin having a siloxane bond (-Si-O-Si-) in the main chain and an organic group in the side chain is included in the "organic compound" in this specification.
  • compound A is an aliphatic compound containing any two or more selected from the group consisting of hydrogen (H), carbon (C) and oxygen (O) in its unit molecular structure, and has the effect of further reducing the friction coefficient for all of the above metal types of the metal material 2. For this reason, it is preferable that the multiple particles 3 contain compound A.
  • compound A include polyolefin resins such as polyethylene and polypropylene, resins obtained by oxidizing these resins (such as oxidized polyethylene), polymethacrylate resins, etc.
  • unit molecular structure means one repeating unit in the case of a polymer, and an individual molecule in the case of a non-polymer.
  • compound B is an aliphatic compound containing one or more amide bonds in its unit molecular structure, and has the effect of sufficiently reducing the friction coefficient for all of the above metal types of metal material 2, and further reducing the friction coefficient of the above metal types except for Ni. Therefore, it is preferable that metal material 2 contains more than 50 mass% in total of one or more metals selected from the group consisting of Al, Ti, Cu, Au, Sn, Zn, and Cr, and that the multiple particles 3 contain compound B.
  • Examples of compound B include nylon resins such as nylon 66 and nylon 12.
  • the compound C is an aromatic compound containing one or more amino groups (-NR 1 R 2 , where R 1 and R 2 are hydrogen or a hydrocarbon group, and R 1 and R 2 may be the same or different) in the unit molecular structure, and has the effect of sufficiently reducing the friction coefficient for all of the above metal species of the metal material 2, and further reducing the friction coefficient of the above metal species except for Zn. That is, it is preferable that the metal material 2 contains more than 50 mass% in total of any one or more metals selected from the group consisting of Al, Ti, Cu, Au, Ni, Sn, and Cr, and the plurality of particles 3 contain the compound C.
  • the compound C include melamine cyanurate, sulfanilic acid, and the like.
  • the plurality of particles 3 preferably have a melting point of 100°C or more or do not exhibit a melting point (i.e., decompose without melting). This makes it possible to suppress the deterioration of the friction coefficient caused by melting of the organic compound when the metal-organic compound composites 1 and 11 are heated to a high temperature. More preferably, the plurality of particles 3 have a melting point of 110°C or more or do not exhibit a melting point, and even more preferably have a melting point of 120°C or more or do not exhibit a melting point.
  • the "melting point” is a melting point obtained by performing thermogravimetric differential thermal analysis (TG-DTA) from room temperature to a maximum of 1000°C at a heating rate of 10°C/min in air, for example.
  • the melting point can be a temperature within a temperature range in which the mass reduction in the TG curve is less than 1%, and a temperature at the intersection of the extrapolated line of the straight line up to the first inflection point where the heat flow rate starts to decrease with the temperature increase in the DTA curve and the extrapolated line of the straight line from the second inflection point onwards where the heat flow rate starts to decrease at a constant gradient (i.e., the straight line with the constant gradient) after the second inflection point where the heat flow rate starts to decrease at a constant gradient thereafter.
  • TG-DTA thermogravimetric differential thermal analysis
  • the decomposition point is preferably 100°C or higher, more preferably 110°C or higher, and even more preferably 120°C or higher.
  • the "decomposition point” is a decomposition point obtained by performing a thermogravimetric differential thermal analysis (TG-DTA) from room temperature to a maximum of 1000°C at a heating rate of 10°C/min in air, for example.
  • TG-DTA thermogravimetric differential thermal analysis
  • the decomposition point can be a temperature within a temperature range in which a mass reduction of 1% or more is confirmed in the TG curve, and a temperature at the intersection of an extrapolated line of a straight line up to the first inflection point where the heat flow rate starts to decrease with increasing temperature in the DTA curve and an extrapolated line of a straight line from the second inflection point onwards where the heat flow rate starts to decrease at a constant gradient (i.e., the straight line with the constant gradient).
  • the decomposition point of the particles 3 is preferably 500°C or less. More preferably, the decomposition point is 450°C or less, and even more preferably, 400°C or less. When the decomposition point is not shown but the combustion point is shown, the combustion point is preferably 500°C or less, more preferably 450°C or less, and even more preferably 400°C or less.
  • the "combustion point” is the combustion point obtained by performing thermogravimetric differential thermal analysis (TG-DTA) from room temperature to a maximum of 1000°C at a heating rate of 10°C/min in the atmosphere, for example.
  • the combustion point can be a temperature within a temperature range in which a mass reduction of 1% or more is confirmed in the TG curve, and a temperature at the intersection of an extrapolated line of a straight line up to the first inflection point where the heat flow rate starts to increase with the temperature increase in the DTA curve and an extrapolated line of a straight line from the second inflection point onwards where the heat flow rate starts to increase at a constant gradient (i.e., the straight line with the constant gradient) can be determined as the combustion point.
  • a constant gradient i.e., the straight line with the constant gradient
  • the multiple particles 3 do not contain fluorine in order to reduce costs.
  • the average particle size (average circle equivalent diameter, median diameter (volume basis)) of the plurality of particles 3 is preferably less than 50 ⁇ m. This can, for example, promote the decomposition of a part of a specific organic compound, and the reaction of a part of the decomposition with the vicinity of the surface 2b of the metal material 2.
  • the average particle size of the plurality of particles 3 is more preferably 30 ⁇ m or less, and even more preferably 10 ⁇ m or less. If the metal material 2 is a surface treatment layer such as a plating layer, the layer surface may become convex if the particle size of the particles 3 is large relative to the layer thickness. If the metal material 2 is a surface treatment layer such as a plating layer, it is preferable that the average particle size of the particles 3 is smaller than the layer thickness, and this makes it possible to improve the dispersion density of the particles 3 per volume in the metal material 2.
  • the plurality of particles 3 are preferably non-conductive. This makes it possible to prevent short circuits in the contacts caused by the conductive particles falling off when the metal-organic compound composites 1 and 11 are used as contact materials.
  • the metal-organic compound composites 1 and 11 may contain other members in order to achieve the object of the present disclosure.
  • the metal-organic compound composites 1 and 11 may contain the substrate thereof.
  • the substrate may be made of metals (or alloys thereof), such as copper, iron, aluminum, titanium, magnesium, etc.
  • the substrate may be in the form of a wrought material such as a plate, strip, bar, shape, or wire, a casting, a sintered material, or a product made by processing these materials into parts.
  • the metal-organic compound composites 1 and 11 may contain organic compound particles other than the specific organic compound particles 3 described above, or may contain inorganic particles.
  • the specific organic compound particles 3 are the specific organic compound particles 3, more preferably 60% or more by volume, 70% or more by volume, 80% or more by volume, or 90% or more by volume, and even more preferably all (100% by volume) are the specific organic compound particles 3.
  • the metal-organic compound composite material 11 according to an embodiment of the present invention can be manufactured by applying a dispersion liquid containing a plurality of organic compound particles 3 to the surface 2b of the metal material 2.
  • a metal-organic compound composite material 1 for example, particles 3 are dispersed in a metal plating solution for a metal material 2, and electroplating is performed on a substrate while stirring, to obtain a metal-organic compound composite material 1 on the substrate in which a plurality of particles 3 are embedded (co-deposited) in the metal material 2.
  • a surfactant may be used as appropriate to prevent the particles 3 from agglomerating in the metal plating solution for the metal material 2 and maintain a stable dispersion state.
  • the particles 3 adsorbed in the initial stage of the reaction are incorporated into the metal material 2, and at the same time, new particles 3 are adsorbed. For this reason, even when the plating process is stopped, in many cases the particles 3 are exposed on the outermost surface, and in a typical eutectoid plating process, a metal-organic compound composite material 1 can be easily produced that includes particles 3 that are partly embedded in the metal material 2 and the remaining part exposed on the surface of the metal material 2.
  • the amount of the particles 3 co-deposited in the metal material 2 is determined by the balance between the frequency of adsorption of (A) and the plating film growth rate of (B).
  • the amount of co-deposition by changing plating conditions such as the amount of particles 3 dispersed in the plating solution. For example, at the end of the plating process, a plating solution that does not contain particles 3 dispersed in the plating solution is used, or the stirring speed of the plating solution is changed to reduce the frequency of adsorption of (A), thereby providing a layer on the outermost surface side of the plating that does not co-deposit the particles 3, and it is possible to produce a metal-organic compound composite material in which the particles 3 are all buried in the metal material 2.
  • the metal-organic compound composites 1 and 11 according to the embodiments of the present invention can improve lubricity (i.e., can reduce the coefficient of friction) compared to the prior art. Specifically, the metal-organic compound composites 1 and 11 according to the embodiments of the present invention can reduce the average value of the coefficient of friction (ratio of horizontal load to vertical load) after each cycle up to 50 cycles in the sliding test described below compared to a metal material in which conventional talc is contacted instead of the particles 3.
  • a mating member which is a ⁇ 6 mm high carbon chromium bearing steel (SUJ2) ball, is slid for a predetermined number of cycles against the surface of the test subject metal-organic compound composite 1 or 11, with a normal load of 1 N applied, a sliding width (sliding stroke) of 10 mm, and an average sliding speed of 30 mm/sec, with one reciprocating motion being defined as one cycle.
  • a ball-on-disk testing device Teribometer manufactured by CSM
  • the metal-organic compound composites 1 and 11 according to the embodiments of the present invention can have even better wear resistance. Specifically, the metal-organic compound composites 1 and 11 according to the embodiments of the present invention can significantly reduce the amount of wear after 500 cycles of the sliding test described above compared to when the particles 3 are not in contact (for example, to 1/2 or less, preferably to 1/5 or less, and more preferably to 1/10 or less).
  • Fe plate plate thickness t: 0.2 mm
  • Al plate plate thickness t: 0.2 mm
  • Ti plate plate thickness t: 0.2 mm
  • Cu plate plate thickness t: 0.3 mm
  • a liquid in which various particles shown in Table 1 were suspended in alcohol at a ratio of 20 mg/ml was dropped at 0.5 ml/ cm2 , and the mixture was dried to obtain a metal-organic compound composite in which various particles were in contact (adhered) to the metal material surface.
  • the above-mentioned Cu plate was used as a substrate, and plating layers of Au, Sn, Zn, Ni, Ni-P (Ni content: 85% by mass or more), and Cr were formed by a known method (plating thickness t: 5 ⁇ m, purity of each plating layer was 95% by mass or more), and a liquid in which various particles (or particle dispersions) shown in Table 1 were suspended in alcohol at a rate of 20 mg/ml was dropped on the Cu plate at 0.5 ml/cm 2 and dried to obtain a metal-organic compound composite material in which various particles contacted (attached) to the metal material surface.
  • thermogravimetric differential thermal analysis was performed on the various particles shown in Table 1 from room temperature to a maximum of 1000° C. at a heating rate of 10° C./min in air using a differential type differential thermobalance (Rigaku Corporation, Thermo plus EVOII), and the melting point, decomposition point, and combustion point of each particle were obtained. The results are also shown in Table 1.
  • the plurality of particles were in contact with (attached to) the surface of the metal material without the metal material being exposed between the plurality of particles on the surface of the metal-organic compound composite material (i.e., the surface of the metal material was covered with the plurality of particles). Furthermore, in all of the metal-organic compound composite materials prepared as described above, the particles in contact with (attached to) the metal material can be peeled off by, for example, pressing the adhesive side of cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No.
  • FIG. 2A shows a photograph of the surface of a metal-organic compound composite in which polyethylene oxide particles are contacted (attached) to the surface of a metal material (Ni-P plating layer). As shown in Fig. 2A, no metallic luster is observed in the part where the particles are attached (part surrounded by a dashed line), and no exposure of the metal material is confirmed.
  • FIG. 2B shows a photograph of the metal-organic compound composite material of FIG.
  • FIG. 2A after cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No. 405) has been applied to the surface of the material (the tape is applied in the area surrounded by the dashed line), and FIG. 2C shows a photograph of the material after the tape has been peeled off in a direction perpendicular to the surface to which it was applied.
  • the cellophane adhesive tape was applied by pressing its adhesive side with a finger against the surface of the metal-organic compound composite material that had come into contact with the particles.
  • FIG. 2C a new metallic luster can be seen in the area where the tape had been applied (area surrounded by the dashed line), indicating that the particles have been peeled off by the cellophane adhesive tape.
  • the metal-organic compound composite material prepared as described above was subjected to the following lubricity evaluation.
  • the following lubricity evaluation was performed using a separately prepared sample set in which the cellophane adhesive tape was not attached or peeled off.
  • a reciprocating sliding test using a ball-on-disk testing device (Tribometer manufactured by CSM), a counter material, which was a ⁇ 6 mm high carbon chromium bearing steel material (SUJ2) ball, was slid against a metal-organic compound composite material to be tested for 50 cycles, with one reciprocating movement being defined as one cycle, with an applied vertical load of 1 N, a sliding width (sliding stroke) of 10 mm, and an average sliding speed of 30 mm/sec.
  • Table 2 can be interpreted as follows: In Table 2, when the metal material is Al, Ti, Cu, Au, Ni, Ni-P, Sn, Zn or Cr, and the particles in contact are polyethylene oxide (meeting the requirements of compound A according to an embodiment of the present invention), polypropylene (meeting the requirements of compound A according to an embodiment of the present invention), nylon 12 (meeting the requirements of compound B according to an embodiment of the present invention), or melamine cyanurate (meeting the requirements of compound C according to an embodiment of the present invention), all of them satisfy the requirements stipulated in the embodiments of the present invention, and the friction coefficient is lower and lubricity is improved compared to when no particles are contacted and when using the conventional technology (i.e., when talc is contacted with the metal material).
  • the metal material is Al, Ti, Cu, Au, Ni, Ni-P, Sn, Zn or Cr
  • the particles in contact are polyethylene oxide (meeting the requirements of compound A according to an embodiment of the present invention), polyprop
  • the metal material is Al, Ti, Cu, Au, Ni, Ni-P, Sn, Zn or Cr, and the particles brought into contact are compound A (polyethylene oxide or polypropylene).
  • the metal material is Al, Ti, Cu, Au, Ni-P, Sn, Zn or Cr, and the particles brought into contact are compound B (nylon 12).
  • the metal material is Al, Ti, Cu, Au, Ni, Ni-P, Sn or Cr, and the particles brought into contact are compound C (melamine cyanurate).
  • the following abrasion resistance evaluation was performed on some of the above metal-organic compound composites.
  • the following abrasion resistance evaluation was performed by separately preparing a sample set that was not subjected to the above cellophane adhesive tape attachment and peeling, and lubricity evaluation.
  • ⁇ Wear resistance evaluation> In a reciprocating sliding test using a ball-on-disk testing device (Tribometer manufactured by CSM), a counter material, which was a ⁇ 6 mm high carbon chromium bearing steel material (SUJ2) ball, was slid against a test subject metal-organic compound composite material for 500 cycles, with one reciprocating movement being defined as one cycle, with an applied vertical load of 1 N, a sliding width (sliding stroke) of 10 mm, and an average sliding speed of 30 mm/sec. After the rotary sliding test, a surface profile was obtained using a surface profile measuring device (DEKTAK6M, manufactured by ULVAC, Inc.) to calculate the amount of wear.
  • DEKTAK6M surface profile measuring device
  • Fig. 3A shows a schematic surface diagram of a sample that was subjected to a reciprocating sliding test
  • Fig. 3B shows, as an example, the surface profile result obtained by measuring the center of the sliding mark 30 shown in Fig. 3A with a surface roughness meter in a direction perpendicular to the sliding direction after a reciprocating sliding test was performed on the metal material: Ni-P (no particles) in Table 1.
  • the wear amount ( ⁇ m 2 ) was calculated by subtracting the area of the raised portion 31b that is considered to have been raised upward by plastic deformation from the area of the worn portion 31a that was scraped below the average line 32a of the non-sliding portion 32 (other than the sliding portion 31) in the surface profile result in Fig. 3B.
  • the results of the wear calculation are shown in Table 3.
  • a plating layer of Ni-P (Ni content: 85% by mass or more) was formed by a known method (plating thickness t: 5 ⁇ m, plating layer purity: 95% by mass or more), and a liquid in which polyethylene oxide particles shown in Table 1 were suspended in alcohol at a ratio of 2 mg/ml was dropped onto the Cu plate at 0.5 ml/ cm2 and dried, thereby obtaining a metal-organic compound composite material in which the polyethylene oxide particles were in contact with (attached to) the surface of the metal material (Ni-P plating layer).
  • Figure 4 shows a photograph of the surface of a metal-organic compound composite in which polyethylene oxide particles have been brought into contact with (attached to) the surface of the metal material (Ni-P plating layer) prepared as described above.
  • metallic luster e.g., the area surrounded by the dashed line
  • part of the Ni-P plating layer was exposed on the surface of the metal-organic compound composite.
  • the metal-organic compound composite in which the metal material (Ni-P plating layer) prepared as described above was brought into contact with polyethylene oxide particles, was evaluated for lubricity in the same manner as in Example 1, and the average friction coefficient showed an excellent value of 0.17.
  • a pure copper plate having a thickness of 0.3 mm was used as a plating substrate, and the surface was degreased by washing with acetone. Then, a sulfuric acid-based Sn plating solution was used, and organic compound particles (addition amount 30 g/L) and a surfactant (AGC Seimi Chemical's Surflon S231, addition amount 5 g/L) shown in Table 4 were dispersed in the plating solution, and while stirring, a current was passed for 10 minutes at a current density of 1 A/ dm2 with the Sn plate as the counter electrode, to obtain a metal-organic compound composite material in which a plurality of organic compound particles were co-deposited (embedded) in a Sn plating layer having a thickness of about 5 ⁇ m such that at least a part of the metal material was exposed on the surface.
  • a metal material (Sn plating layer) was also produced that was plated without dispersing organic compound particles and surfactant.
  • the particles shown in Table 4 were subjected to thermogravimetric differential thermal analysis (TG-DTA) at a heating rate of 10°C/min from room temperature to a maximum of 1000°C in air using a differential thermobalance (Rigaku Corporation, Thermo plus EVOII), to determine the melting point, decomposition point, and combustion point of the particles.
  • TG-DTA thermogravimetric differential thermal analysis
  • the metal-organic compound composite material prepared as described above was subjected to a lubricity evaluation and a wear resistance evaluation in the same manner as in Example 1. The results are shown in Tables 5 and 6, respectively.
  • the above metal-organic compound composite was a preferred embodiment in which the metal material was Al, Ti, Cu, Au, Ni, Ni-P, Sn, Zn or Cr and the particles in contact (embedded) were compound A (crosslinked PMMA), and therefore, compared to the case without particles, the average friction coefficient was reduced to 50% or less compared to the case without particles in contact (embedded), which was an excellent result. Furthermore, from the results in Table 6, it was found that when the requirements of the embodiment of the present invention are met, the amount of wear can be significantly reduced compared to when particles are not in contact with the metal material (when no particles are present).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Lubricants (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Powder Metallurgy (AREA)

Abstract

Ce matériau composite métal/composé organique contient : un matériau métallique comprenant un métal prescrit à plus de 50 % en masse au total; et une pluralité de particules de composé organique. La pluralité de particules de composé organique possède un ou plusieurs états choisis dans le groupe constitué par un état dans lequel les particules sont fixées à la surface du matériau métallique de telle sorte qu'elles peuvent être décollées par un ruban adhésif en cellophane et un état dans lequel les particules sont incorporées dans le matériau métallique de telle sorte qu'au moins une partie du matériau métallique est exposée sur la surface. La pluralité de particules de composé organique contient un ou plusieurs éléments choisis dans le groupe constitué par le composé A, le composé B et le composé C. Le composé A est un composé aliphatique ayant une unité structurale moléculaire contenant au moins deux éléments choisis dans le groupe constitué par l'hydrogène, le carbone et l'oxygène. Le composé B est un composé aliphatique ayant une unité structurale moléculaire contenant une ou plusieurs liaisons amide. Le composé C est un composé aromatique ayant une unité structurale moléculaire contenant un ou plusieurs groupes amino.
PCT/JP2023/033566 2022-09-29 2023-09-14 Matériau composite métal/composé organique WO2024070735A1 (fr)

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JP2003277950A (ja) * 2002-03-25 2003-10-02 Nippon Parkerizing Co Ltd 金属材料の塑性加工用表面処理方法
JP2004339338A (ja) * 2003-05-15 2004-12-02 Sumika Plastech Co Ltd ポリオレフィン炭化物およびその製造方法
JP2008248294A (ja) * 2007-03-29 2008-10-16 Furukawa Electric Co Ltd:The 潤滑性粒子を有するめっき材料、その製造方法およびそれを用いた電気・電子部品
JP2013129902A (ja) * 2011-12-22 2013-07-04 Om Sangyo Kk めっき品及びその製造方法
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WO2020184270A1 (fr) * 2019-03-12 2020-09-17 三井化学株式会社 Composition de résine polyamide ignifuge
JP2020164621A (ja) * 2019-03-29 2020-10-08 株式会社オートネットワーク技術研究所 潤滑剤、電気接点、コネクタ端子、およびワイヤーハーネス
JP2021063188A (ja) * 2019-10-16 2021-04-22 株式会社エムエイチセンター 塑性加工用潤滑剤
JP2022020762A (ja) * 2017-05-11 2022-02-01 デュポン ポリマーズ インコーポレイテッド ポリマー金属ハイブリッド物品

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5032244A (fr) * 1973-07-20 1975-03-28
JPH0617296A (ja) * 1992-07-02 1994-01-25 Sumitomo Metal Ind Ltd 成形性に優れた複合めっきＡｌ板の製造方法
JP2003277950A (ja) * 2002-03-25 2003-10-02 Nippon Parkerizing Co Ltd 金属材料の塑性加工用表面処理方法
JP2004339338A (ja) * 2003-05-15 2004-12-02 Sumika Plastech Co Ltd ポリオレフィン炭化物およびその製造方法
JP2008248294A (ja) * 2007-03-29 2008-10-16 Furukawa Electric Co Ltd:The 潤滑性粒子を有するめっき材料、その製造方法およびそれを用いた電気・電子部品
JP2013129902A (ja) * 2011-12-22 2013-07-04 Om Sangyo Kk めっき品及びその製造方法
JP2022020762A (ja) * 2017-05-11 2022-02-01 デュポン ポリマーズ インコーポレイテッド ポリマー金属ハイブリッド物品
JP2019171613A (ja) * 2018-03-27 2019-10-10 日鉄日新製鋼株式会社 塗装金属素形材、複合体および複合体の製造方法
WO2020184270A1 (fr) * 2019-03-12 2020-09-17 三井化学株式会社 Composition de résine polyamide ignifuge
JP2020164621A (ja) * 2019-03-29 2020-10-08 株式会社オートネットワーク技術研究所 潤滑剤、電気接点、コネクタ端子、およびワイヤーハーネス
JP2021063188A (ja) * 2019-10-16 2021-04-22 株式会社エムエイチセンター 塑性加工用潤滑剤

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